U.S. patent number 10,533,106 [Application Number 15/561,712] was granted by the patent office on 2020-01-14 for non-newtonian white inks.
This patent grant is currently assigned to Hewlett-Packard Development Company, L.P.. The grantee listed for this patent is Hewlett-Packard Development Company, L.P.. Invention is credited to Paul Joseph Bruinsma, Thomas W. Butler, Vladek Kasperchik.
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United States Patent |
10,533,106 |
Kasperchik , et al. |
January 14, 2020 |
Non-Newtonian white inks
Abstract
The present disclosure provides an example where a non-Newtonian
white ink can include an aqueous ink vehicle, from 5 wt % to 60 wt
% of white colorant, and from 0.1 wt % to 5 wt % of amphoteric
alumina particles dispersed in the aqueous ink vehicle. The white
colorant can include white metal oxide pigment having an average
particulate size from 100 nm to 2,000 nm, an alumina coating on the
white metal oxide pigment forming an alumina-coated pigment, and a
polymeric dispersant associated with a surface of the
alumina-coated pigment. The amphoteric alumina particles can have
an average particles size from 2 nm to less than 100 nm.
Inventors: |
Kasperchik; Vladek (Corvallis,
OR), Bruinsma; Paul Joseph (San Diego, CA), Butler;
Thomas W. (Corvallis, OR) |
Applicant: |
Name |
City |
State |
Country |
Type |
Hewlett-Packard Development Company, L.P. |
Fort Collins |
CO |
US |
|
|
Assignee: |
Hewlett-Packard Development
Company, L.P. (Spring, TX)
|
Family
ID: |
57835035 |
Appl.
No.: |
15/561,712 |
Filed: |
July 20, 2015 |
PCT
Filed: |
July 20, 2015 |
PCT No.: |
PCT/US2015/041184 |
371(c)(1),(2),(4) Date: |
September 26, 2017 |
PCT
Pub. No.: |
WO2017/014747 |
PCT
Pub. Date: |
January 26, 2017 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20180086933 A1 |
Mar 29, 2018 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09C
1/3692 (20130101); C09D 11/38 (20130101); C09C
1/00 (20130101); C09D 11/326 (20130101); C09C
1/3661 (20130101); C09D 11/322 (20130101); C09D
11/54 (20130101); C09C 1/043 (20130101); C09C
3/063 (20130101); C09C 1/3669 (20130101); C09D
11/106 (20130101); C01P 2004/64 (20130101); C01P
2004/62 (20130101) |
Current International
Class: |
C09D
11/54 (20140101); C09D 11/106 (20140101); C09D
11/322 (20140101); C09D 11/326 (20140101); C09C
3/06 (20060101); C09C 1/36 (20060101); C09D
11/38 (20140101); C09C 1/00 (20060101); C09C
1/04 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
1784462 |
|
May 2007 |
|
EP |
|
2243807 |
|
Oct 2010 |
|
EP |
|
2004124077 |
|
Apr 2004 |
|
JP |
|
2005298802 |
|
Oct 2005 |
|
JP |
|
2011225867 |
|
Nov 2011 |
|
JP |
|
2012241057 |
|
Dec 2012 |
|
JP |
|
5519112 |
|
Jun 2014 |
|
JP |
|
9718268 |
|
May 1997 |
|
WO |
|
2007124120 |
|
Nov 2007 |
|
WO |
|
2012054052 |
|
Apr 2012 |
|
WO |
|
2012170032 |
|
Dec 2012 |
|
WO |
|
2013162513 |
|
Oct 2013 |
|
WO |
|
2014193387 |
|
Dec 2014 |
|
WO |
|
WO 2016/175871 |
|
Nov 2016 |
|
WO |
|
WO 2018/190848 |
|
Oct 2018 |
|
WO |
|
Other References
"Ti-Pure R-960 Datasheet" from The Chemours Company TT, LLC, 2015;
2 pages;
https://www.chemours.com/Titanium_Technologies/en_US/assets/downlo-
ads/Ti-Pure-R-960-coatings-product-information.pdf. cited by
examiner .
"DuPont Ti-Pure R-960 Datasheet" from The Chemours Company TT, LLC,
2012; 1 page;
https://www.chemours.com/Titanium_Technologies/en_US/products/960-
/Ti-Pure_R-960_datasheet_H65960-8_022912.pdf. cited by examiner
.
International Search Report and Written Opinion dated Nov. 17, 2015
for PCT/US2015/041184; Applicant Hewlett-Packard Development
Company L.P. cited by applicant.
|
Primary Examiner: Klemanski; Helene
Attorney, Agent or Firm: Thorpe North & Western LLP
Claims
What is claimed is:
1. A non-Newtonian white ink, comprising: an aqueous ink vehicle;
from 5 wt % to 60 wt % of white colorant, comprising: white metal
oxide pigment having an average particulate size from 100 nm to
2,000 nm, an alumina coating on the white metal oxide pigment
forming an alumina-coated pigment, and a polymeric dispersant
associated with a surface of the alumina-coated pigment; and from
0.1 wt % to 5 wt % of amphoteric alumina particles dispersed in the
aqueous ink vehicle, wherein the amphoteric alumina particles have
an average particles size from 2 nm to less than 100 nm.
2. The non-Newtonian white ink of claim 1, wherein the alumina
coating further comprises silica.
3. The non-Newtonian white ink of claim 1, wherein the
non-Newtonian white ink comprises 5 wt % to 50 wt % white metal
oxide pigment, 0.05 wt % to 10 wt % alumina in the alumina coating,
0.005 wt % to 5 wt % polymeric dispersant; and from 0.5 wt % to 3
wt % amphoteric alumina particles having an average particle size
from 5 nm to 30 nm.
4. The non-Newtonian white ink of claim 1, wherein the white metal
oxide pigment includes titanium dioxide particles, zinc oxide
particles, zirconium oxide particles, or combinations thereof.
5. The non-Newtonian white ink of claim 1, wherein the
non-Newtonian white ink further comprises latex particles having a
glass transition temperature from -20.degree. C. to 130.degree.
C.
6. The non-Newtonian white ink of claim 1, wherein the polymeric
dispersant includes a non-ionic or predominantly non-ionic
dispersant defined by an acid number not higher than 100 mg KOH/g
based on dry polymer weight, and wherein the polymeric dispersant
further comprises an anionic anchoring group attached to the
alumina coating.
7. The non-Newtonian white ink of claim 1, wherein the polymeric
dispersant further includes an anionic dispersant defined by having
an acid number higher than 100 mg KOH/g based on dry polymer weight
attached to the alumina coating.
8. The non-Newtonian white ink of claim 1, wherein the
non-Newtonian white ink is in an agitated state so that the white
colorant and the amphoteric alumina particles are fully suspended
in the non-Newtonian white ink.
9. The non-Newtonian white ink of claim 1, wherein the white
colorant and the amphoteric alumina particles are in the form of a
weakly associated flocculated mass upon settling of solids in the
non-Newtonian white ink.
10. A method of making a non-Newtonian white ink, comprising:
milling a mixture of a white metal oxide pigment having an alumina
coating and a polymeric dispersant in a water-based carrier to form
a pigment dispersion; combining ink vehicle with the pigment
dispersion to form a white ink with suspended white colorant; and
adding amphoteric alumina particles to the mixture, the pigment
dispersion, the white ink, or combination thereof.
11. The method of claim 10, further comprising allowing the
non-Newtonian white ink to destabilize causing the suspended white
colorant and the amphoteric alumina particles to form a flocculated
mass.
12. The method of claim 10, further comprising admixing latex
particles to the mixture, the pigment dispersion, the white ink, or
combination thereof, wherein the non-Newtonian white ink comprises:
from 5 wt % to 60 wt % of the suspended white colorant having an
average particle size from 100 nm to 2,000 nm; from 0.05 wt % to 15
wt % of the alumina coating; from 0.005 wt % to 5 wt % of the
polymeric dispersant; from 0.1 wt % to 5 wt % alumina particles
having an average particle size from 2 nm to less than 100 nm; and
from 2 wt % to 30 wt % of the latex particles having a glass
transition temperature from -20.degree. C. to 130.degree. C.
13. A fluid set for inkjet imaging, comprising: a non-Newtonian
white ink, comprising: an aqueous ink vehicle, from 5 wt % to 60 wt
% of white colorant, comprising: white metal oxide pigment having
an average particulate size from 100 nm to 2,000 nm, an alumina
coating on the white metal oxide pigment forming an alumina-coated
pigment, and a polymeric dispersant associated with a surface of
the alumina-coated pigment, and from 0.1 wt % to 5 wt % of
amphoteric alumina particles dispersed in the aqueous ink vehicle
having an average particle size from 2 nm to less than 100 nm; and
a fixer fluid, comprising: aqueous fixer vehicle, and from 0.1 wt %
to 25 wt % cationic polymer.
14. The fluid set of claim 13, wherein the non-Newtonian white ink
is formulated for inkjet application upon agitation to resuspend
white colorant and the amphoteric alumina particles, and wherein
the fixer fluid is formulated for inkjet application having a
viscosity from 1 cP to 35 cP at 25.degree. C.
15. The fluid set of claim 13, wherein the non-Newtonian white ink
is formulated for inkjet application upon agitation to resuspend
white colorant and the amphoteric alumina particles, and wherein
the fixer fluid is formulated for analog application having a
viscosity from 1 cP to 500 cP at 25.degree. C.
16. The fluid set of claim 13, wherein the alumina coating of the
non-Newtonian white ink further comprises silica.
17. The fluid set of claim 13, wherein the non-Newtonian white ink
comprises 5 wt % to 50 wt % white metal oxide pigment, 0.05 wt % to
10 wt % alumina in the alumina coating, 0.005 wt % to 5 wt %
polymeric dispersant; and from 0.5 wt % to 3 wt % amphoteric
alumina particles having an average particle size from 5 nm to 30
nm.
18. The fluid set of claim 13, wherein: the white metal oxide
pigment includes titanium dioxide particles, zinc oxide particles,
zirconium oxide particles, or combinations thereof, the
non-Newtonian white ink further comprises latex particles having a
glass transition temperature from -20.degree. C. to 130.degree. C.,
or both.
19. The fluid set of claim 13, wherein the polymeric dispersant
includes a non-ionic or predominantly non-ionic dispersant defined
by an acid number not higher than 100 mg KOH/g based on dry polymer
weight, and wherein the polymeric dispersant further comprises an
anionic anchoring group attached to the alumina coating.
20. The fluid set of claim 13, wherein the polymeric dispersant
further includes an anionic dispersant defined by having an acid
number higher than 100 mg KOH/g based on dry polymer weight
attached to the alumina coating.
Description
BACKGROUND
The use of inkjet printing systems has grown dramatically in recent
years. This growth may be attributed to desirability in print
resolution and overall print quality coupled with appreciable
reduction in cost. Today's inkjet printers offer acceptable print
quality for many commercial, business, and household applications
at lower costs than comparable products available just a few years
ago. Notwithstanding their recent success, research and development
efforts continue toward advancing inkjet print quality over a wide
variety of different applications, but there remain challenges.
BRIEF DESCRIPTION OF THE DRAWINGS
Additional features and advantages of the disclosure will be
apparent from the detailed description which follows, taken in
conjunction with the accompanying drawings, which together
illustrate, by way of example, features of the present
technology.
FIG. 1A depicts dispersed white metal oxide pigment, and FIG. 1B
depicts typical settling that occurs with white metal oxide
pigment, such as TiO.sub.2, over a short amount of time;
FIG. 1C depicts an example white metal oxide pigment, such as
TiO.sub.2, with a cationic alumina surface coated by dense layer of
two different types of polymeric dispersant in accordance with
examples of the present disclosure;
FIG. 1D depicts white metal oxide pigment prepared in accordance
with examples of the present disclosure that is co-dispersed with
amphoteric alumina particles, and FIG. 1E depicts settling that
occurs over time to form flocculated masses in accordance with
examples of the present disclosure;
FIG. 2 depicts examples where a cationic polymer formulation is
digitally printed on a media substrate contemporaneously or just
before printing a non-Newtonian white inkjet ink thereon, and
wherein the non-Newtonian white inkjet ink is prepared in
accordance with examples of the present disclosure;
FIG. 3 depicts examples where a cationic polymer is applied to a
media substrate prior to (either digital or by analog application)
printing a non-Newtonian white inkjet ink thereon, and wherein the
non-Newtonian white inkjet ink is prepared in accordance with
examples of the present disclosure;
FIG. 4 depicts examples of heat drying and fusing an image printed
in as described in FIG. 2 or 3 in accordance with examples of the
present disclosure;
FIG. 5 depicts a printed article, such as that shown in FIG. 4,
after heat fusing on the media substrate in accordance with
examples of the present disclosure;
FIG. 6 is a flow chart describing a method of making a
non-Newtonian white ink in accordance with examples of the present
disclosure;
FIG. 7 is a graph depicting the effect pH has on alumina in
accordance with examples of the present disclosure;
FIG. 8 is a graph depicting the non-Newtonian nature of white
pigment dispersions prepared in accordance with examples of the
present disclosure; and
FIG. 9 is a graph depicting the non-Newtonian characteristic of
white inks prepared in accordance with examples of the present
disclosure.
Reference will now be made to certain technology examples
illustrated, and specific language will be used herein to describe
the same. It will nevertheless be understood that no limitation of
the scope of the disclosure is thereby intended.
DETAILED DESCRIPTION
Certain pigments can be more challenging than other in achieving
certain desirable printing and jetting properties. For example, ink
opacity corresponding to white color appearance can be more
difficult to achieve for white inks compared to black, magenta, or
cyan inks. Additionally, high colorant loads and large pigment
particle sizes can lead to settling that clogs inkjet printheads
and other microchannels. More specifically, the combination of high
bulk densities and larger particle sizes tend to lead to high
settling rates of the pigment in water-based inkjet ink
formulations, and these larger and denser pigments can form a
sediment very rapidly, e.g., within a few days. Once the sediment
has formed, the gravitational forces tend to lead to a tight
compaction or cemented sediment, which is very challenging to
resuspend, plugging printheads and microchannels, etc. Prolonged
stirring or shaking may not be sufficient to break down the
aggregated particles in the sediment to unclog blocked channels and
restore the settled ink to its original useable state. Furthermore,
irreversible pigment settling can also reduce print quality because
the formation of non-redispersible pigment sediment depletes bulk
pigment concentration in the ink liquid portion that remains,
compromising print opacity. In a more extreme case, settling in a
manner where resuspension cannot be achieved may even render the
ink substantially transparent.
Thus, the present disclosure is drawn to white inks, including
water-based white inkjet inks, that can be jetted from various
types of inkjet printheads, but which can also be particularly
friendly for use in thermal inkjet printheads. These inks, in some
instances with the assistance of a fixer coating layer or fixer
ink, can be printed not only on porous media, but also effectively
on more challenging non-porous polymer media.
The non-Newtonian white inks of the present disclosure address
issues related to system reliability and print opacity performance
of white inks that use relatively large and dense white metal oxide
pigment particles. To illustrate, high bulk density of white metal
oxide pigment, such as TiO.sub.2, which have a relatively large
particle size, e.g., from 100 nm to 2000 nm, from 150 nm to 750 nm,
or from 200 nm to 500 nm, can be used to provide high opacity
performance. However, the high bulk density, e.g., about 4.2 for
the rutile form, and large size also can result in fast settling of
the pigment in low viscosity water-based inkjet ink formulations.
More specifically, TiO.sub.2 particles (See FIG. 1A) can easily
agglomerate resulting in a sediment (See FIG. 1B) that is difficult
to break apart, e.g., layers with very strong inter-particle
cohesion are formed. This can clog fluidic pathways of ink delivery
systems and inkjet printheads, rendering the printing device
non-operational within few days.
Because it can be difficult to completely eliminate settling of
large dense particles in low viscosity environments, reducing
settling rate or allowing for settling in a manner that produces a
more easily resuspendable sediment provides a good solution. For
example, as shown in FIG. 1C, an example white metal oxide pigment
12, such as TiO.sub.2, is coated with a cationic alumina (in some
examples, also with silica) surface 14 by dense layer of two
different types of polymeric dispersant, namely an adsorbed
non-ionic or predominantly non-ionic polymer dispersant of a
comb-type structure with anionic or acidic anchor group 16a, as
well as an anionic dispersant 16b. Though two dispersants are
shown, it is noted that many examples can be prepared with only one
dispersant, or more than two dispersants. Thus, in accordance with
examples of the present disclosure, white metal oxide pigment can
be treated with alumina (with or without silica) to form a coating,
and the coated pigment can be further dispersed with a polymeric
dispersing agent with added alumina particles also included therein
(See FIG. 1D). This formulation does not stop gravitational
settling, but rather, provides conditions where a loose flocculated
mass of pigment and alumina particles (See FIG. 1E) are formed that
can be easily resuspended with minor agitation or shaking.
Essentially, by milling alumina-coated white metal oxide pigment
with the polymeric dispersant and by adding amphoteric alumina
particles, the various particles form flocs or flocculated masses
that allow for a more controlled destabilization of the pigment in
the aqueous ink vehicle. By allowing sedimentation of the weakly
associated colloid particles to occur (as loose flocs or
flocculated masses), a fluffy sediment of low density is formed
that can be easily resuspended without permanent clogging of the
inkjet printhead and/or fluid channels. Thus, when settling, more
benign flocculated masses of white metal oxide pigment form (rather
than tightly packed pigment that is unrecoverable).
In further detail, dispersions of white pigment prepared as
described herein can be co-dispersed or formulated with added
amphoteric alumina particles to form white inks, and in the white
inks. As a note, certain amphoteric aluminum oxide nano-particles
which have both cationic and anionic sites when exposed to aqueous
environment over a wide pH range can be used as added particles in
the white inks of the present disclosure. Surface hydroxyl groups
of such aluminum oxides may adsorb protons and form cationic sides,
as follows: AlOH+H.sup.+.fwdarw.AlOH.sup.2+ On the other hand
surface hydroxyls may be also deprotonated and form anionic sites:
AlOH+OH.sup.-.fwdarw.AlO.sup.-+H.sub.2O
The distribution of surface charges on nano-particles of some
amphoteric aluminum oxides may be anisotropic. This behavior is
especially pronounced for aluminum oxo-hydroxide AlO(OH), also
known as boehmite. This is because boehmite nano-particles in
aqueous dispersions can easily aggregate into complex network of
structures. TEM evidence of aggregation of boehmite nano-particles
into continuous 3-dimensional network (viewed under magnification,
e.g., .about.200K) indicates the formation of these structures.
Furthermore, boehmite nano-particles, and other alumina particles,
can attach or adsorb to a surface of metal oxide particles,
including white metal oxide pigments described herein, to further
assist with achieving the flocculated masses described herein.
In further detail, alumina particles, such as boehmite
nano-particles, can self-aggregate and adsorb to surface of large
white metal oxide particles and can further be suspended in a white
ink for providing controlled destabilization of white ink
formulations. To illustrate, titanium dioxide (TiO.sub.2) pigment
particles in ink formulation can agglomerated into loose flocs as
shown previously in FIG. 1E where a network of amphoteric alumina
oxide particles with large pigment particles become trapped inside
the network. Settling of these loose flocs or flocculated masses
produces loose low-density sediment with very weak mechanical
properties. Minor agitation, such as might occur with ink
recirculation in the inkjet printer printhead and/or ink supplies
can be sufficient for quick system recovery into an operational
state after long term inactivity.
In accordance with this, the present disclosure is drawn to a
non-Newtonian white ink, including an aqueous ink vehicle, from 5
wt % to 60 wt % of white colorant, and from 0.1 wt % to 5 wt % of
amphoteric alumina particles having an average particle size from 2
nm to less than 100 nm. The white colorant can include white metal
oxide pigment having an average particulate size from 100 nm to
2,000 nm, an alumina coating on the white metal oxide pigment
forming an alumina-coated pigment, and a polymeric dispersant
associated with a surface of the alumina-coated pigment. In one
example, the alumina coating includes silica as well as alumina. In
one example, the non-Newtonian white ink can further include from 2
wt % to 30 wt % of latex particles. In another specific example,
the white metal oxide pigment can have a refractive index of 1.8 to
3.0, a bulk density from 3.0 to 4.5. Thus, since this size of
pigment and this bulk density of pigment tends to settle rather
quickly, by coating the white metal oxide pigment with alumina and
associating the surface with polymeric dispersant, and by adding
amphoteric alumina particles, when settling does occur, the white
colorant can be easily resuspended from the white flocculated
colorant mass in preparation for inkjet application. Thus, when
resuspended, a homogenous or evenly distributed pigment dispersion
can be readily formed from the flocculated colorant mass.
Regarding the non-Newtonian white ink, in one example, the alumina
coating can further include silica. In another example, the
non-Newtonian white ink can include 5 wt % to 50 wt % white metal
oxide pigment, 0.05 wt % to 10 wt % alumina in the alumina coating,
0.005 wt % to 5 wt % polymeric dispersant; and from 0.5 wt % to 3
wt % amphoteric alumina particles having an average particle size
from 5 nm to 30 nm. In another example, the white metal oxide
pigment can include titanium dioxide particles, zinc oxide
particles, zirconium oxide particles, or combinations thereof. In
yet another example, the non-Newtonian white ink can further
include latex particles having a glass transition temperature from
-20.degree. C. to 130.degree. C. In another example, the polymeric
dispersant can include a non-ionic or predominantly non-ionic
dispersant defined by an acid number not higher than 100 mg KOH/g
based on dry polymer weight, and wherein the polymeric dispersant
further includes an anionic anchoring group attached to the alumina
coating; and in one ore specific example, the polymeric dispersant
can further include an anionic dispersant defined by having an acid
number higher than 100 mg KOH/g based on dry polymer weight
attached to the alumina coating. In another example, the
non-Newtonian white ink can be in an agitated state so that the
white colorant and the amphoteric alumina particles are fully
suspended in the non-Newtonian white ink. In still another example,
the white colorant and the amphoteric alumina particles can be in
the form of a weakly associated flocculated mass upon settling of
solids in the non-Newtonian white ink.
A method of making a non-Newtonian white ink can include milling a
mixture of a white metal oxide pigment having an alumina coating
and a polymeric dispersant in a water-based carrier to form a
pigment dispersion, combining ink vehicle with the pigment
dispersion to form a white ink with suspended white colorant, and
adding amphoteric alumina particles to the mixture, the pigment
dispersion, the white ink, or combination thereof. In one example,
the method can include allowing the non-Newtonian white ink to
destabilize causing the suspended white colorant and the amphoteric
alumina particles to form a flocculated mass.
In further detail, the method can include allowing the
non-Newtonian white ink to destabilize causing the suspended white
colorant and the amphoteric alumina particles to form a flocculated
mass. In another example, the method can include admixing latex
particles to the mixture, the pigment dispersion, the white ink, or
combination thereof, wherein the non-Newtonian white ink includes
from 5 wt % to 60 wt % wt % of the suspended white colorant having
an average particle size from 100 nm to 2,000 nm; from 0.05 wt % to
15 wt % of the alumina coating; from 0.005 wt % to 5 wt % of the
polymeric dispersant; from 0.1 wt % to 5 wt % alumina particles
having an average particle size from 2 nm to less than 100 nm; and
from 2 wt % to 30 wt % of the latex particles having a glass
transition temperature from -20.degree. C. to 130.degree. C.
A fluid set for inkjet imaging can include a non-Newtonian white
ink and fixer fluid. The non-Newtonian white ink can include an
aqueous ink vehicle, from 5 wt % to 60 wt % white colorant, and
from 0.1 wt % to 5 wt % of amphoteric alumina particles having an
average particle size from 2 nm to less than 100 nm. The white
colorant can include white metal oxide pigment having an average
particulate size from 100 nm to 2,000 nm, an alumina coating on the
white metal oxide pigment forming an alumina-coated pigment, and a
polymeric dispersant associated with a surface of the
alumina-coated pigment. The fixer fluid can include aqueous fixer
vehicle, and from 0.1 wt % to 25 wt % cationic polymer.
The fixer fluid can be formulated for inkjet application, or for
analog application, e.g., rolling, brushing, curtain coating, blade
coating, Meyer rod coating, etc. For example, the non-Newtonian
white ink can be formulated for inkjet application upon agitation
to resuspend white colorant and the amphoteric alumina particles,
and the fixer fluid can be formulated for inkjet application having
a viscosity from 1 cP to 35 cP at 25.degree. C. Alternatively, the
non-Newtonian white ink can be formulated for inkjet application
upon agitation to resuspend white colorant and the amphoteric
alumina particles, and the fixer fluid is formulated for analog
application having a viscosity from 1 cP to 500 cP at 25.degree.
C.
In certain specific examples, other ranges of ingredients can be
used, such as, independently, from 5 wt % to 50 wt % white metal
oxide pigment, from 0.05 wt % to 10 wt % alumina in the alumina
coating, from 0.005 wt % to 5 wt % polymeric dispersant; and/or
from 0.5 wt % to 3 wt % amphoteric alumina particles having an
average particle size from 5 nm to 30 nm.
These white non-Newtonian inks or dispersion can be prepared with
good sediment redispersibility, and can be prepared by milling base
white metal oxide pigment, e.g., TiO.sub.2, powder where the
pigment is coated with a gel-sol coating of alumina in water-based
slurry containing about 20 wt % to about 70 wt % of the
pigment/alumina particles and dispersant(s). For example, a
non-ionic dispersant with an anionic anchoring group can be present
at from 0.5 wt % to 4 wt % (of dry pigment weight), and if two
dispersants are present, such as in the case of an anionic
dispersant, this dispersant content can be at from 0.1 wt % to 1 wt
% (of dry pigment weight). Milling can be carried out until a
desired mean pigment particle size is achieved, such as at a size
where appropriate light-scattering may occur. Other example ranges
and/or component choices can likewise be selected in accordance
with the disclosed technology.
As a note, a white ink or a white dispersion used to prepare the
white ink can have "non-Newtonian" or "shear thinning" properties
in relation to higher concentrations of weakly bound agglomerates
or flocculated masses. For example, a non-Newtonian ink or
dispersion may be defined such that the viscosity of an ink or
dispersion measured at 10 sec.sup.-1 shear rate is at least 10%
higher than the viscosity of the ink or dispersion when measured at
shear rate of 1000 sec.sup.-1 at 25.degree. C. Or, for example, a
non-Newtonian ink or dispersion may have a viscosity measured at 10
sec.sup.-1 shear rate that is at least 20% higher, 30% higher, 50%
higher, 100% higher (2.times.), etc. than the viscosity of the ink
or dispersion when measured at shear rate of 1000 sec.sup.-1 at
25.degree. C. In many examples, the shear rate difference can be
much higher than 2 times, e.g., 5 times, 10 times, 20 times, etc.
Thus, a white ink, depending on the concentration of pigment (with
alumina coating and polymeric dispersant) and amphoteric alumina
particles, can have a non-Newtonian character when the "colorant"
and amphoteric alumina particles are in the form of a flocculated
mass, and the non-Newtonian properties are reduced when the
colorant is re-suspended in preparation for inkjet application, for
example.
In further detail, when preparing the non-Newtonian white ink from
the pigment/alumina/dispersant slurry, ink vehicle components can
be added, such as water, organic co-solvent, surfactant, etc., to
form the non-Newtonian white ink having from 5 wt % to 60 wt %
colorant mass, from 10 wt % to 50 wt % colorant mass, from 15 wt %
to 45 wt % colorant mass, from 20 wt % to 40 wt % colorant mass,
from 10 wt % to 25 wt % colorant mass, from 5 wt % to 20 wt %
colorant mass, from 10 wt % to 20 wt % colorant mass, etc., either
in flocculated or resuspended form.
Furthermore, the amphoteric alumina particles, such as boehmite,
can be added to the formulation either prior to milling, during
milling, or after milling. If after milling, then the amphoteric
alumina particles can be added prior to, at the same time, or after
the addition of ink vehicle components. Notably, some of the ink
vehicle components are initially part of the pigment dispersion,
e.g., water and/or other ingredients that become part of the ink
vehicle when additional ink vehicle components are added for
finalizing the ink for use.
These non-Newtonian white inks can be used in forming white images
on various media substrate, including smooth polymer (non-porous)
media substrate, and can be printed in combination, as mentioned,
with a fixer coated on the surface of the media. For example, a
fixer with cationic polymer can be applied to the media substrate
and can be formulated so that its cationic polymer interacts with
any anionically charged components in the non-Newtonian white ink
to immobilize the white metal oxide pigment.
In each of these examples, there are several advantages related to
the inclusion of the modified white metal oxide pigment and the
amphoteric alumina particles. For example, as mentioned, these
solids allow for a controlled destabilization of the pigment in the
aqueous ink vehicle, e.g., allowing weakly associated sedimentation
of colloid particles to occur (as loose flocs) such that fluffy
sediment of lower density flocs can be easily resuspended.
Furthermore, as mentioned, these solids may also cooperate with
other solids, e.g., the latex particles, to act as a spacer between
white metal oxide pigment particles, thereby enhancing white print
opacity, as will be described herein in greater detail.
FIG. 2 depicts an example where a digitally printed fixer is
applied just prior to or essentially simultaneously with a white
inkjet ink of the present disclosure. FIG. 3 depicts an example
where a fixer is applied to a media substrate prior to application
of an inkjet ink. The fixer in this latter example can likewise be
applied by digital printing, or alternatively, by analog
application, e.g., rolling, brushing, curtain coating, blade
coating, Meyer rod coating, or any other coating methodology
suitable for producing thin layer of fixer on the printed
substrate, etc. As shown in FIGS. 2 and 3, an inkjet printing
device 30 is provided to digitally print a white inkjet ink 10, and
in some examples, a fixer composition 20 on a media substrate 40.
The media substrate can be a smooth, non-porous polymer substrate
that is otherwise difficult to print on with high image quality and
high durability. Specifically, FIG. 2 shows the fixer composition
being printed digitally from the printing device, and FIG. 3 shows
the fixer composition being pre-applied to the media substrate,
either digitally or by an analog coating method. In both examples,
the non-Newtonian white inkjet ink includes suspended white
colorant that includes a white metal oxide pigment 12 with an
alumina coating 14 and associated with polymeric dispersants
16a,16b. In this specific example, there are two types of polymeric
dispersants, namely a non-ionic or predominantly non-ionic
dispersant 16a and a short-chained anionic dispersant 16b, but this
is not required. Latex particles 18 are also shown in the ink, all
suspended by an aqueous ink vehicle, which typically includes
water, organic co-solvent, and the like. Additionally, amphoteric
alumina particles 19 are also co-dispersed therewith to assist in
providing non-Newtonian or sheer thinning behavior to the white
ink. Regarding the fixer composition 20, this formulation can
include cationic polymer 22 dissolved in a fixer vehicle, wherein
the cationic polymer is interactive with the suspended white
colorant or other anionic components that may be found in the
non-Newtonian white ink, thereby providing some immobilization or
freezing of the pigment and particles on the print media
substrate.
In another example, the image printed or otherwise generated in
accordance with FIGS. 2 and 3 can be heat fused. More specifically,
FIG. 4 shows a heat fusing device 50 which is used to apply heat 52
to the printed article to form a heat fused printed article as
shown in FIG. 5. Because of the presence of both the alumina
coating 14, the amphoteric alumina particles 19, and the latex
particles 18 (heat fused as a non-continuous mass with other
polymers that may be present) providing spacing between white metal
oxide pigment particles 12, there can be enhanced light scattering
60 and lower transmittance 62 than even more densely packed white
metal oxide pigment, which thus provides enhanced opacity. This
increased opacity can be achieved by optically spacing the white
metal oxide pigment from one another. For example, because of the
relative high refractive index of the white metal oxide pigment and
the relative low refractive index optical spacing provided by the
alumina, latex, etc., the opacity of the printed coating can be
boosted by from 0.1% to 25%, or more typically from 5% to 20% or
from 5% to 25% compared to an inks without optical spacing
material. In other words, the crowding effect of tightly-packed
high refractive index (n) particles with little or no voids
decreases light scattering and increase transparency of the
coating. By optically spacing the white metal oxide pigment with
the low refractive index materials (and typically heat fusing the
latex after printing), an increase in opacity can be realized. As a
further point, fusion can add enhanced durability to the printed
article. In some cases, the fusing of the latex particles may help
the latex polymer distribute more evenly between light scattering
white metal oxide pigment particles and, hence, further enhance
opacity as well. That, in combination with the presence of the
alumina coating, can provide desirable results.
In accordance with this, a printed article can include up to 80
gsm, or up to 50 gsm, of a total fluids (white ink+fixer) applied
to a media substrate. The term "up to 80 gsm" is used because
typical inkjet images include fully imaged areas as well as
non-imaged and/or lower density areas. After water and solvent(s)
evaporation and fusing, the gsm roughly translates into 15-50 wt %
of the initial fluid dispersion flux density, i.e. thus less than
60 gsm. In one example, full density inked area may be at from 30
to 60 gsm ink/fixer film, but densities lower in the tone ramp will
be lower than this, thus the use of the phrase "up to" 75 gsm or
"up to" 60 gsm. That being stated, though some areas on a media
substrate might be at 0 gsm under this definition (unprinted
areas), there will be areas that are imaged that range from greater
than 0 gsm up to 60 gsm (after drying or heat fusing). In a typical
printed article, there is a portion of the media that can be
printed at from 5 gsm to 60 gsm.
Turning now to the various specific ingredients that are present in
the non-Newtonian white ink, one of the ingredients included in the
non-Newtonian white ink is a dispersion of amphoteric alumina
particles, such as boehmite. A variety of water-dispersible alumina
nano-powders and commercially available premade alumina dispersions
can be used in the formulations. In some examples, the amphoteric
alumina particles can have a particle size in the ink that is
smaller than that of white metal oxide pigment, e.g., from 2 nm to
100 nm, from 2 nm to 50 nm, from 2 nm to 25 nm, or from 10 nm to
about 15 nm, on average. For example, when using water-dispersible
dry powders, a stock alumina nano-particle dispersion may be
produced by milling the powder in aqueous environment at a pH from
about 3.5 to about 5. The nano-particles can be premilled and added
to the white ink, or can be milled with the alumina-coated white
metal oxide pigment and polymeric dispersant.
In one example, a suitable alumina (boehmite) nano-particle
dispersion can be prepared by milling Disperal.RTM. alumina powder
(available from Sasol GmbH) in an Ultra Apex.RTM. Mill UAM-015
(available from Kotobuki Industries Co., Ltd). loaded with 50 .mu.m
YTZ beads. The milled slurry can include about 10 wt % to 40 wt %
(or about 2 wt %) of the Disperal.RTM. alumina, in some examples.
The particle size of the alumina after the milling can result
ranging from about 10 nm to about 13 nm, on average.
As mentioned, there is also white metal oxide pigment present that
is coated with an alumina coating and dispersed with a polymeric
dispersant. The "white" pigment provides much of the white
coloration to the ink, though without the other ingredients in the
ink, individual pigment particles may have some transparency or
translucency. Examples of white metal oxide pigments that can be
used include titanium dioxide particles, zinc oxide particles,
zirconium oxide particles, combinations thereof, or the like. In
one specific example, the white metal oxide pigment can be titanium
dioxide (TiO.sub.2), and even more specifically, rutile. Thus, the
non-Newtonian white inks of the present disclosure are based on
transparent metal oxide pigment particles with very high refractive
index, that when spaced appropriately, provide very opaque and
white print layers.
Pigments with high light scattering capabilities, such as these,
can be selected to enhance light scattering and lower
transmittance, thus increasing opacity. White metal oxide pigments
can have a particulate size from about 100 nm to 2,000 nm, or from
150 nm to about 1,000 nm, or more typically, from about 150 nm to
750 nm, and in still another example, from about 180 nm to 400 nm.
The combination of these pigments within these size ranges,
appropriately spaced from one another with ingredients such as the
alumina coating, amphoteric alumina particles, and latex particles,
high opacity can be achieved at relatively thin thickness, e.g., 5
gsm to 60 gsm or 5 gsm to 50 gsm after removal of water and other
solvent(s) from the printed ink and fixer film.
Regarding the alumina coating that can be applied to the white
metal oxide pigment, any of a number of alumina compositions can be
used. The alumina can be coated on the pigment by precipitation
from a liquid phase, and in some examples, there are commercially
available alumina-containing TiO.sub.2 pigments (or other white
metal oxide pigments) that can be used. These commercially
available pigments which include alumina can be milled with
polymeric dispersant, as described in greater detail hereinafter.
Essentially, however, when alumina and white metal oxide pigment is
co-milled with polymeric dispersant in an aqueous environment, a
large number of gel-coat particles can be formed, similar to that
shown in FIGS. 1C and 1D. As a side note, alumina coatings need not
be only alumina. In some examples, alumina coatings can include
other materials, such as silica.
The amount of free gel-coat particles produced in these dispersions
during the milling process can be dependent on the original alumina
content in the commercial pigment formulation. When the number of
gel-coat particles is high enough, the gel-coat particles tend to
compete with uncoated white metal oxide pigment particles for
adsorption of the polymeric dispersant(s). Thus, a large number of
individual alumina or gel-coat particles can use up enough of the
dispersants from liquid phase to start destabilizing or
flocculating the milled pigment particles. On the other hand,
adsorption of anionic or weakly anionic dispersant molecules onto
cationic alumina surface coated TiO.sub.2 or other white metal
oxide pigment particles may reduce overall surface charge pigment.
As a result, in combination with the amphoteric alumina particles,
the pigment particles may start forming weakly bound agglomerates
(flocs) in the liquid phase of ink. Both phenomena usually
manifests itself in increased milled slurry viscosity and its
non-Newtonian (shear-thinning) rheological behavior. Thus, in
accordance with examples of the present disclosure, to achieve the
loose floc formation (or controlled destabilization) that is
desirable, the alumina coated particle content and amphoteric
alumina particle content can be included so as to be high enough to
cause flocs to form when settling over time. White metal oxide
pigment particles in higher gel-coat content dispersions
agglomerate into loose flocs and tend to form voluminous sediments
which can be redispersed easily by fluid agitation, which is
desirable. To describe one specific example, the settling can form
a semi-liquid yogurt-like consistency flocculated mass produced by
settling of milled high gel-coat white metal oxide pigment and
amphoteric alumina particles. For example, alumina-coated pigment
Ti-Pure.RTM. R900 available from DuPont has an alumina content of
about 4.3 wt % based on the pigment content, and thus, when milled
with polymeric dispersant, can form the suspended flocs described
herein, which are easily resuspended. Furthermore, the
non-Newtonian character can be enhanced further by adding
amphoteric alumina particles as described herein. Other
alumina-coated pigments that can be used include, for example,
TR.RTM. 50 (2.6 wt % alumina coating), TR.RTM. 52 (3.4 wt % alumina
coating), TR60 (3.1 wt % alumina coating), TR.RTM. 90 (4 wt %
alumina coating), and TR.RTM. 93 (3.9 wt % alumina coating), each
from Huntsman Chemical; Ti-Pure.RTM. R960 (3.3 wt % alumina
coating) and Ti-Pure.RTM. R931 (6.4 wt % alumina coating), each
available from DuPont; and CR.RTM.-813 (3.5 wt % alumina coating)
and CR.RTM.-828 (3.5 wt % alumina coating), each available from
DuPont. Notably, these coating weight percentages are based on the
pigment weight, and furthermore, silica may also be included with
these coatings at various concentrations either greater than or
less than the alumina content.
To provide some concentration ranges that are useful, raw TiO.sub.2
pigment (or other white metal oxide pigment) coated with an alumina
coating can be prepared with an alumina coating at a total amount
of the gel-coat (either alumina alone or a combination of alumina
and silica) on pigment surface at least at 0.1 wt % based on white
metal oxide pigment weight, at least 0.5 wt % based on white metal
oxide pigment weight, at least 2 wt % based on white metal oxide
pigment weight, or at least 3 wt % based on white metal oxide
pigment weight.
Alumina coated- and polymeric dispersant-modified white metal oxide
pigments produced as described herein can be rendered or formulated
into a non-Newtonian inkjet ink formulation with amphoteric alumina
particles suitable for reliable printing through a thermal inkjet
printhead or other printing system. During long-term inactivity of
such white ink formulations, e.g. found in inkjet printhead and
microfluidic channels as well as in ink supplies, the ink
formulations can form pigment sediment. This settling can be
remedied by short-term agitation and/or recirculation of the
settled ink in the printhead, microfluidic channels, and ink supply
of the printer, which easily recovers the ink to a properly working
or jettable state.
The white metal oxide pigment with alumina coated thereon as part
of a gel-coat, among other solids that may be present, i.e. the
amphoteric alumina particles, can be dispersed by milling the
components together. Typically, the alumina coating on the metal
oxide pigment is co-milled with the polymeric dispersant, and the
amphoteric alumina particles are added afterwards in the ink
formulation, but in some examples, the amphoteric alumina particles
can be added before or during milling.
Regarding the polymeric dispersants per se, any of a number of
polymeric dispersants can be used. For example, a short-chain
anionic dispersant can be used, a non-ionic or predominantly
non-ionic dispersing agent, and/or any other dispersant effective
for dispersing the white metal oxide pigment. Suitable dispersing
agents can allow for dispersibility and stability in an aqueous ink
environment, as well as for contributing to controlled
destabilizing effect (along with the alumina coating) when the
white metal oxide pigment settles and forms a white flocculated
colorant mass. These dispersants can also be prepared to have
little to no impact on the viscosity of the liquid phase of the
ink, as well as retain good printhead reliability in thermal inkjet
printheads (if the ink is a thermal inkjet ink). If the ink is a
piezo inkjet ink, then additional flexibility regarding viscosity
is tolerable. Dispersant of one or various types can each be
present in the inks of the present disclosure at various
concentrations, such as from 0.005 wt % to 5 wt %.
For definitional purposes, "short-chain anionic dispersants" that
can be used include polymeric dispersants with chain length short
enough to impact viscosity of ink formulation at moderate
concentrations, typically having an acid number higher than 100 mg
KOH/g based in dry polymer content. For example, short-chain
anionic dispersants can include dispersants having a weight average
molecular weight lower than 30,000 Mw, or more typically, lower
than 15,000 Mw, e.g., 1,000 Mw to 30,000 Mw, or from 2,000 Mw to
15,000 Mw.
Also for definitional purposes, "non-ionic or predominantly
non-ionic dispersants" include non-ionic dispersants, as well as
only weakly ionic dispersants, i.e. the acid number of the
non-ionic or predominantly non-ionic/weak anionic dispersant, per
dry polymer, is typically not higher than 100 mg KOH/g, and is
typically not higher than 50 mg KOH/g, or even not higher than 30
mg KOH/g. That being stated, in one example, non-ionic dispersing
agent with no anionic properties can be used. These non-ionic or
predominantly non-ionic dispersants can range in average molecular
weight from 500 Mw to 50,000 Mw, in certain examples.
Turning now to the short-chain anionic dispersants, examples
include polymers and/or oligomers with low weight average molecular
weight. More specifically, low molecular weight (Mw) short-chain
anionic dispersants can include acrylic and methacrylic acids
homopolymers such as polyacrylic acid (PAA), polymethacrylic acid
(PMAA), or their salts. More specific examples include, but are not
limited to, Carbosperse.RTM. K-7028 (PAA with M.about.2,300),
Carbosperse.RTM. K-752 (PAA with M.about.2,000), Carbosperse.RTM.
K-7058 (PAA with M.about.7,300), Carbosperse.RTM. K-732 (PAA with
M.about.6,000), Carbosperse.RTM. K-752 (Na salt of PMAA with
M.about.5,000), all available from Lubrizol Corporation. Others
include Dispex.RTM. AA 4935 available from BASF Dispersions &
Pigments Division, as well as Tamol.RTM. 945 available from Dow
Chemical. Low molecular weight acrylic and methacrylic acid
co-polymers with other carboxylic monomer moieties can also be
used, such as co-polymers of acrylic and maleic acids available
from Kelien Water Purification Technology Co. Low molecular weight
co-polymers of carboxylic acid monomers with other water-soluble
non-carboxylic acidic monomer moieties, such as sulfonates,
styrenesulfonates, phosphates, etc., can also be used. Examples of
such dispersants include, but are not limited to, Carbosperse.RTM.
K-775 and Carbosperse.RTM. K-776 (co-polymers of acrylic and
sulfonic acid), Carbosperse.RTM. K-797, Carbosperse.RTM. K-798, or
Carbosperse.RTM. K-781 (co-polymers of acrylic, sulfonic acid and
styrenesulfonic acid), all available from Lubrizol Corporation.
Additionally, low molecular weight co-polymers of carboxylic acid
monomers with some hydrophobic monomers can likewise be used.
Dispersants from this group are suitable here if their acid number
(content of hydrophilic acidic moieties in polymer chain) is high
enough to make the dispersant well soluble in aqueous phase.
Examples of such dispersants include, but are not limited to
styrene-acrylic acid copolymers such as Joncryl.RTM. 671,
Joncryl.RTM. 683, Joncryl.RTM. 296, or Joncryl.RTM. 690, available
from BASF, as well as other water soluble styrene-maleic anhydride
co-polymer resins.
Referring now to the non-ionic dispersants that can be used,
examples include water-hydrolysable silane coupling agents (SCAs)
with relatively short (oligomer length range of not longer than 50
units, not longer than 30 units, or not longer than 15 units, e.g.,
10 to 15 units) polyether chain(s), which are also soluble in
water. An example of such a dispersant includes Silquest.RTM. A1230
polyethylene glycol methoxysilane available from Momentive
Performance Materials. Other examples include soluble
low-to-midrange M (e.g., usually molecular mass of the polymer less
than 15,000 Da) branched co-polymers of comb-type structures with
polyether pendant chains and acidic anchor groups attached to the
backbone, such as Disperbyk.RTM. 190 and Disperbyk.RTM. 199
available from BYK Chemie, as well as Dispersogen.RTM. PCE
available from Clariant. In one example, one or both of
Cab-O-Sperse.RTM. K-7028 and Disperbyk.RTM. 190 can be used.
In one example, reactive hydrophilic alkoxysilane dispersants that
can be present, and examples include, but are not limited to,
hydrolysable alkoxysilanes with alkoxy group attached to
water-soluble (hydrophilic) moieties, such as water-soluble
polyether oligomer chains, phosphate groups, or carboxylic groups.
In some examples, the dispersant used to disperse the alumina
coated white metal oxide pigment can be a polyether alkoxysilane or
polyether phosphate dispersant. Upon dissolution in water with the
alumina and the white metal oxide pigment, the alkoxysilane group
of the dispersant often hydrolysis resulting in formation of
silanol group. The silanol group, in turn, may react or form
hydrogen bonds with hydroxyl groups of metal oxide particulate
surface, as well as with silanol groups of other dispersant
molecules through hydrogen bonding. These reactions lead to bonding
or preferential absorption of the dispersant molecules to the metal
oxide particulate surfaces and also form bonds between dispersant
molecules themselves. As a result, these interactions can form
thick hydrophilic coatings of reactive dispersant molecules on
surface of the alumina coated white metal oxide pigment. This
coating can increase the hydrodynamic radius of the particles and
thus reduce their effective density and settling rate. Furthermore,
the dispersant coating and the amphoteric alumina particles prevent
agglomeration of the alumina coated white metal oxide pigment upon
settling so that when sediment and settling does occur over time in
the ink formulations, the settled pigment and other particles
remain fluffy and thus are easy to redisperse upon agitation. In
still further detail, these dispersants have a relatively short
chain length and do not contribute significantly to the ink
viscosity, even with relatively high metal oxide particulate loads,
e.g. over 25 wt % white metal oxide pigment in the ink.
As mentioned, a suitable alkoxysilane dispersant can have an
alkoxysilane group which can be easily hydrolyzed in aqueous
environment and produce a silanol group, and a hydrophilic segment.
The general structure of the alkoxysilane group is --Si(OR).sub.3,
where R most can be methyl, ethyl, n-propyl, isopropyl, or even a
longer (branched or unbranched) alkane chain. It is noted that the
longer the hydrocarbon (R), the slower hydrolysis rate and rate of
interaction with dispersed metal oxide particulate surface. In a
few highly practical examples, structures with --Si(OR).sub.3 where
R is methyl or ethyl can typically be used. The hydrophilic segment
of the alkoxysilane dispersant can likewise be large enough
(relative to the whole molecule size) in order to enable dispersant
solubility in aqueous environment, as well as prevent agglomeration
of the alumina coated white metal oxide pigment and amphoteric
alumina particles. In one example, the hydrophilic segment can be a
polyether chain, e.g., polyethylene glycol (PEG) or its co-polymer
with polypropylene glycol (PPG). Polyether-based dispersant
moieties have clean thermal decomposition, and thus, are good
candidates for use. When heated above decomposition temperature,
PEG and PPG-based molecules decompose into smaller molecular
fragments with high volatility or good water solubility. Thus,
their decomposition usually does not form noticeable amounts of
solid residue on surface of microscopic heaters used for driving
thermal inkjet printheads (which can cause thermal inkjet
printheads to fail over time or render them non-operational in some
instances).
In further detail, examples polyether alkoxysilane dispersants that
may be used to disperse alumina coated white metal oxide pigment
can be represented by the following general Formula (I):
##STR00001## wherein: a) R.sup.1, R.sup.2 and R.sup.3 are hydroxy
groups, or hydrolyzable linear or branched alkoxy groups. For
hydrolyzable alkoxy groups, such groups can have 1 to 3 carbon
atoms; in one aspect, such groups can be --OCH.sub.3 and
--OCH.sub.2CH.sub.3. In some examples, R.sup.1, R.sup.2 and R.sup.3
are linear alkoxy groups having from 1 to 5 carbon atoms. In some
other examples, R.sup.1, R.sup.2 and R.sup.3 groups are --OCH.sub.3
or --OC.sub.2H.sub.5. b) PE is a polyether oligomer chain segment
of the structural formula [(CH.sub.2).sub.n--CH(R)--O].sub.m,
attached to Si through Si--C bond, wherein n is an integer ranging
from 0 to 3, wherein m is an integer superior or equal to 2 and
wherein R is H or a chain alkyl group. R can also be a chain alkyl
group having 1 to 3 carbon atoms, such as CH.sub.3 or
C.sub.2H.sub.5. In some examples, m is an integer ranging from 3 to
30 and, in some other examples, m is an integer ranging from 5 to
15. The polyether chain segment (PE) may include repeating units of
polyethylene glycol (PEG) chain segment (--CH.sub.2CH.sub.2--O--),
or polypropylene glycol (PPG) chain segment
(--CH.sub.2--CH(CH.sub.3)--O--), or a mixture of both types. In
some examples, the polyether chain segment (PE) contains PEG units
(--CH.sub.2CH.sub.2--O--); and c) R.sup.4 is hydrogen, or a linear
or a branched alkyl group. In some examples, R.sup.4 is an alkyl
group having from 1 to 5 carbon atoms.
Other examples of dispersants used to disperse alumina coated white
metal oxide pigment can include polyether alkoxysilane dispersants
having the following general Formula (II):
##STR00002## wherein R', R'' and R''' are linear or branched alkyl
groups. In some examples, R', R'' and R''' are linear alkyl groups
having from 1 to 3 carbon atoms in chain length. In some examples,
R', R'' and R'''--CH.sub.3 or --C.sub.2H.sub.5. R.sup.4 and PE are
as described above for Formula (I); i.e. PE is a polyether oligomer
chain segment of the structural formula:
[(CH.sub.2).sub.n--CH--R--O].sub.m, wherein n is an integer ranging
from 0 to 3, wherein m is an integer superior or equal to 2 and
wherein R is H or a chain alkyl group; and R.sup.4 is hydrogen, or
a linear or a branched alkyl group. In some examples, R.sup.4 is
CH.sub.3 or C.sub.2H.sub.5.
In some examples, the alumina coated white metal oxide pigment
present in the ink compositions are dispersed with polyether
alkoxysilanes. Examples of suitable polyether alkoxysilanes include
(CH.sub.3O).sub.3Si--(CH.sub.2CH.sub.2O).sub.n, H;
(CH.sub.3CH.sub.2O).sub.3Si--(CH.sub.2CH.sub.2O).sub.n, H;
(CH.sub.3O).sub.3Si--(CH.sub.2CH.sub.2O).sub.n, CH.sub.3;
(CH.sub.3CH.sub.2O).sub.3Si--(CH.sub.2CH.sub.2O).sub.n, CH.sub.3;
(CH.sub.3O).sub.3Si--(CH.sub.2CH.sub.2O).sub.n, CH.sub.2CH.sub.3;
(CH.sub.3CH.sub.2O).sub.3Si--(CH.sub.2CH.sub.2O).sub.n,
CH.sub.2CH.sub.3;
(CH.sub.3O).sub.3Si--(CH.sub.2CH(CH.sub.3)O).sub.n, H;
(CH.sub.3CH.sub.2O).sub.3Si--(CH.sub.2CH(CH.sub.3)O).sub.n, H;
(CH.sub.3O).sub.3Si--(CH.sub.2CH(CH.sub.3)O).sub.n, CH.sub.3;
(CH.sub.3CH.sub.2O).sub.3Si--(CH.sub.2CH(CH.sub.3)O).sub.n,
CH.sub.3; wherein n' is an integer equal to 2 or greater. In some
examples, n' is an integer ranging from 2 to 30 and, in some other
examples, n' is an integer ranging from 5 to 15.
Commercial examples of the polyether alkoxysilane dispersants
include, but are not limited to, the aforementioned
Silquest.RTM.A-1230 manufactured by Momentive Performance
Materials, and Dynasylan.RTM. 4144 manufactured by
Evonik/Degussa.
The amount of dispersant used to disperse the alumina coated white
metal oxide pigment and other solids may vary from about 0.3% by
weight to about 300% by weight of the white metal oxide pigment
content. In some examples, the dispersant content range is from
about 0.5 to about 150% by weight of the white metal oxide pigment
content. In some other examples, the dispersant content range is
from about 5 to about 100% by weight of the white metal oxide
pigment content.
A dispersion of white metal oxide pigment suitable for forming the
non-Newtonian white inks of the present disclosure can be prepared
via milling or dispersing metal oxide powder in water in the
presence of suitable dispersants and alumina. For example, the
metal oxide dispersion may be prepared by milling commercially
available inorganic oxide pigment with alumina coating (having a
large particulate size, e.g., even in the micron range) in the
presence of a polymeric dispersant, or by milling of white oxide
pigment coated with alumina-rich gel-coat, until the desired
particulate size is achieved. The starting dispersion to be milled
can be an aqueous dispersion with solid content up to 65% by weight
of the white metal oxide pigment. The milling equipment that can be
used may be a bead mill, which is a wet grinding machine capable of
using very fine beads having diameters of less than 1.0 mm (and,
generally, less than 0.5 mm) as the grinding medium, for example,
Ultra-Apex Bead Mills from Kotobuki Industries Co. Ltd, or
MiniCer.RTM. bead mill (available from NETZSCH Premier
Technologies, LLC, Exton, Pa.). The milling duration, rotor speed,
and/or temperature may be adjusted to achieve the dispersion
particulate size desired. In one example, the polymeric dispersant
can include a short-chain anionic dispersant or a non-ionic or
predominantly non-ionic dispersant, or both. Thus, the polymeric
dispersant can be co-milled with the alumina-coated white metal
oxide pigment, thereby modifying both the surface of white metal
oxide pigment and physical character of the alumina (creating a
coating of alumina on the reduced size white metal oxide pigment).
The freshly milled surface and coating can thus be highly accepting
of the polymeric dispersant.
It is also notable that there can be some advantages to adding the
latex particles to the inks of the present disclosure. For example,
by combining the modified white metal oxide pigment (modified by
alumina coating and polymeric dispersant) with latex particles,
opacity can be increased further. In one aspect, a white metal
oxide pigment to latex particulate weight ratio can be from 6:1 to
1:3. In certain specific examples, by selecting white metal oxide
pigment with a high refractive index (e.g. from 1.8 to 2.8), and
latex particles with a relatively lower refractive index (e.g.,
from 1.3 to 1.6), the opacity of the ink when printed on a media
sheet can be unexpectedly increased further compared to an ink
without the added latex particles.
Furthermore, the latex particles (at high enough concentration) can
form continuous polymer phase after the ink printing and
drying/curing. This polymer phase can bind rigid particles into
continuous coating with good mechanical durability, i.e. act as a
binder phase. In the absence of the binder in these ink
formulations, the printed layer would may not have as much
mechanical durability (reduced rub resistance, etc.). In one
example, a latex dispersion may be produced by emulsion
polymerization or co-polymerization of acrylic and styrene
monomers. The list of suitable monomers can include (but is not
limited to) C1 to C8 alkyl methacrylates and alkyl acrylates,
styrene and substituted methyl styrenes, polyol acrylates and
methacrylates such as hydroxyethyl acrylate, acrylic acid,
methacrylic acid, polymerizable surfactants, or the like.
The monomers used in the latexes can also be vinyl monomers. In one
example, the monomers can be vinyl monomers (such as vinyl
chloride, vinylidene chloride, etc.), vinyl ester monomers,
acrylate monomers, methacrylate monomers, styrene monomers,
ethylene, maleate esters, fumarate esters, itaconate esters, or
mixtures thereof. In one aspect, the monomers can include
acrylates, methacrylates, styrenes, or mixtures thereof. The
monomers can likewise include hydrophilic monomers including acid
monomers as mentioned, as well as hydrophobic monomers.
Furthermore, monomers that can be polymerized in forming the
latexes include, without limitation (some of which being previously
mentioned), styrene, .alpha.-methyl styrene, p-methyl styrene,
methyl methacrylate, hexyl acrylate, hexyl methacrylate, butyl
acrylate, butyl methacrylate, ethyl acrylate, ethyl methacrylate,
propyl acrylate, propyl methacrylate, 2-ethylhexyl acrylate,
2-ethylhexyl methacrylate, octadecyl acrylate, octadecyl
methacrylate, stearyl methacrylate, vinylbenzyl chloride, isobornyl
acrylate, tetrahydrofurfuryl acrylate, 2-phenoxyethyl methacrylate,
benzyl methacrylate, benzyl acrylate, ethoxylated nonyl phenol
methacrylate, isobornyl methacrylate, cyclohexyl methacrylate,
trimethyl cyclohexyl methacrylate, t-butyl methacrylate, n-octyl
methacrylate, lauryl methacrylate, trydecyl methacrylate,
alkoxylated tetrahydrofurfuryl acrylate, isodecyl acrylate,
isobornylmethacrylate, isobornyl acrylate, dimethyl maleate,
dioctyl maleate, acetoacetoxyethyl methacrylate, diacetone
acrylamide, N-vinyl imidazole, N-vinylcarbazole,
N-vinyl-caprolactam, combinations thereof, derivatives thereof, or
mixtures thereof.
Acidic monomers that can be polymerized in forming latexes include,
without limitation, acrylic acid, methacrylic acid, ethacrylic
acid, dimethylacrylic acid, maleic anhydride, maleic acid,
vinylsulfonate, cyanoacrylic acid, vinylacetic acid, allylacetic
acid, ethylidineacetic acid, propylidineacetic acid, crotonoic
acid, fumaric acid, itaconic acid, sorbic acid, angelic acid,
cinnamic acid, styrylacrylic acid, citraconic acid, glutaconic
acid, aconitic acid, phenylacrylic acid, acryloxypropionic acid,
aconitic acid, phenylacrylic acid, acryloxypropionic acid,
vinylbenzoic acid, N-vinylsuccinamidic acid, mesaconic acid,
methacroylalanine, acryloylhydroxyglycine, sulfoethyl methacrylic
acid, sulfopropyl acrylic acid, styrene sulfonic acid,
sulfoethylacrylic acid, 2-methacryloyloxymethane-1-sulfonic acid,
3-methacryoyloxypropane-1-sulfonic acid,
3-(vinyloxy)propane-1-sulfonic acid, ethylenesulfonic acid, vinyl
sulfuric acid, 4-vinylphenyl sulfuric acid, ethylene phosphonic
acid, vinyl phosphoric acid, vinyl benzoic acid,
2-acrylamido-2-methyl-1-propanesulfonic acid, combinations thereof,
derivatives thereof, or mixtures thereof.
In one specific example, the acidic monomer content in the latex
mix can range from 0.1 wt % to 15 wt % and the balance being
non-acidic monomers, with suitable latex particle sizes range from
50 nm to 300 nm. Glass transition temperatures may range from
-20.degree. C. to 130.degree. C. The latex content in the
non-Newtonian white ink formulations, when present, may range from
2 wt % to 30 wt %, or from 3 wt % to 20 wt %, or more typically
from 5 wt % to 15 wt %.
As mentioned, the particulate size of the white metal oxide pigment
can be from 100 nm to 1,000 nm, but in other examples, the
particulate size can be from 125 nm to 700 nm, from 150 nm to 500
nm, or 180 nm to 400 nm. These larger sized particles are
considered to be efficient particulate sizes for light scattering
when spaced appropriately by the alumina coating, amphoteric
alumina particles, and the latex particles. The more efficient the
light scattering, typically, the more opaque the printed ink layer
may be (assuming appropriate spacing in the pigmented layer as
described herein). Thus, the non-Newtonian white inks of the
present disclosure can be formulated such that when printed, the
alumina coating, amphoteric alumina particles, and latex particles
provide an average space between white metal oxide pigment ranging
from 20 nm to 1,000 nm, in one example. In other examples, the
average space between white metal oxide pigment can be 50 nm to 500
nm, from 50 to 300, or in one specific example, about 50 nm to 250
nm.
In further detail, optical spacing can be experimentally evaluated
by printing the ink on a media substrate, and when a latex is
present, fusing the ink by applying heat at a temperature about
2.degree. C. to 110.degree. C. above the minimum film formation
temperature of the latex particles, and evaluating using Transition
Electron Microscopy (TEM) cross-section photo of a printed white
ink layer after drying. If the opacity provided by the
non-Newtonian white ink is not high enough, the ratio of white
metal oxide pigment to latex particles can be adjusted up or down,
as effective, or the thickness of the ink can be increased. That
being stated, an advantage of the non-Newtonian white inks of the
present disclosure is that in some instances, thickness does not
need to be increased to increase opacity. For example, by
appropriately spacing the white metal oxide pigment and latex
particles, opacity can be boosted from 0.1% to 25%, and more
typically, from 5% to 25%.
In addition to assisting with enhanced opacity, as briefly
mentioned, the latex particles can also provide enhanced
durability. More specifically, the use of latex particles,
including fusible latex particles that are thermally or otherwise
cured after printing on the media substrate, can provide added
durability to the printed image. Thus, the latex can provide the
dual role of assisting the alumina coating in enhancing opacity by
appropriately spacing the white metal oxide pigment, and can also
provide durability on the printed media sheet. This is particularly
the case in examples where there may be high metal oxide
particulate loads that are dispersed by appropriate dispersing
agents. Films formed by hard ceramic particles such as high
refractive index metal oxides on surface of low porosity and
non-porous media substrates tend to have very poor mechanical
properties. The film-forming behavior of latex particles described
herein can bind the relatively large white metal oxide pigment
(with dispersing agent present in the ink) into continuous coating
that can be very durable. Additionally, as mentioned, the low
refractive index of the polymer film along with the alumina coating
creates low refractive index or "n" domains, i.e. optical spacers
between high n white metal oxide pigment particles, thereby
enhancing opacity of the print.
Coalescence of latex particles into continuous phase creates low
refractive index domains in the coating. The refractive index of
the fused latex in the coating may range from 1.3 to 1.65, and in
one example, can be from 1.4 to 1.6, or 1.4 to 1.5. That, in
conjunction with the alumina (or alumina and silica) coating with a
refractive index ranging from 1.4 to 1.65 is contrasted with the
white metal oxide pigment particles which have a refractive index
ranging from 1.8 to 2.8, or from 2.2 to 2.8. Specific examples
include zinc oxide (about 2.4), titanium dioxide (about 2.5 to
2.7), zirconium oxide (about 2.4), etc. Typically, the difference
in the refractive indexes can be from about 0.2 to 1.5, or more, if
possible (typically, the higher is the better), though this is not
always the case, as long as there is enough of a difference that
the opacity can be increased at least to some degree by the optical
spacing and the refractive index difference.
The latexes can have various shapes, sizes, and molecular weights.
In one example, polymer in the latex particles may have a weight
average molecular weight (Mw) of about 5,000 Mw to about 500,000
Mw. In one aspect, the latex particles can have a weight average
molecular weight (Mw) ranging from about 100,000 Mw to about
500,000 Mw. In some other examples, the latex resin has a weight
average molecular weight of about 150,000 Mw to 300,000 Mw.
The non-Newtonian white inks described herein are very useful for
inkjet application, including thermal inkjet application. In one
example, a reactive hydrophilic alkoxysilane dispersant can be used
to assist in particulate dispersion and jettability. These or other
dispersants can be short-chain anionic, or non-ionic or
predominantly non-ionic in nature. In some specific examples,
inkjet printing of white coatings or patterns with adequate opacity
(>50-60%) can benefit from a relatively high pigment load (e.g.
white metal oxide pigment above 2 wt %, above 5 wt %, above 8 wt %,
etc.). Jetting of high pigment load (particularly with other
solids) inks becomes challenging even for piezo printheads.
However, with the use of an appropriate dispersant, such as the
non-ionic or predominantly non-ionic dispersants described herein,
more reliable performance of higher metal oxide particulate loads
printed from thermal inkjet printheads with low nominal drop weight
(as low as 10 ng, or even as low as 5 ng) can be realized.
Turning now to the fixer fluid that may be used with the
non-Newtonian white inks of the present disclosure, cationic
polymer can be added to various ink or liquid vehicles to form
fixer fluids of various viscosities for various application
processes. Cationic polymers that may be used can include
guanidinium or fully quaternized ammonium functionalities, such as
quaternized polyamine copolymers. In one example, the cationic
polymer might not contain primary or secondary ammonium
functionalities, such as polyallylamine or polyethylene imine.
Generally, for some digital application processes, i.e. thermal
inkjet application, the weight average molecular weight (Mw) of the
cationic polymer allows viscosity of 1 cP to 25 cP at 25.degree.
C., 1 cP to 15 cP at 25.degree. C., or 1 cP to 10 cP at 25.degree.
C., as measured on a Brookfield viscometer. Though viscosity
outside of this range can be used, particularly for piezo inkjet
applications or for analog (non-digital printing) applications,
e.g., 1 cP to 35 cP at 25.degree. C. (for piezo inkjet) and 1 cP to
500 cP at 25.degree. C. for analog applications. Typical weight
average molecular weight for the cationic polymer can be less than
500,000 Mw, and in one aspect, less than 50,000 Mw. In another
example, cationic polymers can have high charge densities to
enhance fixing efficiencies. As such, cationic charge densities can
be higher than 1000 microequivalents per gram cationic
functionality. In one aspect, higher than 4000 microequivalents per
gram can be used. Additionally, concentrations can be low to avoid
regulatory issues with aquatic toxicity, e.g., from 0.1 wt % to 25
wt %, and in one aspect, 1 wt % to 5 wt %, or in another aspect,
from 1 wt % to 2.5 wt %.
In additional detail, classes of cationic polymers that can be used
include, but are not limited to, quaternized polyamines,
dicyandiamide polycations, diallyldimethyl ammonium chloride
copolymers, quaternized dimethylaminoethyl(meth)acrylate polymers,
quaternized vinylimidizol polymers, alkyl guanidine polymers,
alkoxylated polyethylene imines, and mixtures thereof. It is to be
understood that one or multiple polycations may be used, and that
any desirable combination of the polycations can be used. One or
multiple ions of the cationic polyelectrolytes may be ion-exchanged
for a nitrate, acetate, mesylate, or other ion. As a non-limiting
example, one material is Floquat.RTM. FL2350, a quaternized
polyamine derived from epichlorohydrin and dimethyl amine,
commercially available from SNF Inc.
Typical ink vehicle or fixer vehicle formulations described herein
can include water and other ingredients, depending on the
application method desired for use. For example, when jetting the
ink or fixer, the formulation may include water as well as
co-solvents present in total at from 0.1 wt % to 50 wt %, though
amounts outside of this range can also be used. Further,
surfactants can be present, ranging from 0.01 wt % to 10 wt %. The
balance of the formulation can further include or other vehicle
components known in the art, such as biocides, viscosity modifiers,
materials for pH adjustment, sequestering agents, preservatives,
and the like. Typically, the ink vehicle can include water as one
of a major solvent and can be referred to as an aqueous liquid
vehicle. It is noted that the fixer fluid may be formulated for
inkjet application or for analog coating processes, and thus, the
ingredients and concentrations for such different applications can
vary widely. For example, a thicker slurry may be used for analog
application, or a less viscous fluid may be used for digital
application.
Apart from water, the ink vehicle can include high boiling solvents
and/or humectants such as aliphatic alcohols, aromatic alcohols,
diols, glycol ethers, polyglycol ethers, 2-pyrrolidinones,
caprolactams, formamides, acetamides, and long chain alcohols.
Examples of such compounds include but are not limited to
2-pyrrolidinone and 2-methyl-1,3-propanediol. The concentration
range for high boiling solvents and/or humectants in the ink can be
from 0.1 wt % to 30 wt %, depending on the printhead jetting
architecture, though amounts outside of this range can also be
used.
Classes of co-solvents that can be used can include organic
co-solvents including aliphatic alcohols, aromatic alcohols, diols,
glycol ethers, polyglycol ethers, 2-pyrrolidinones, caprolactams,
formamides, acetamides, and long chain alcohols. Examples of such
compounds include primary aliphatic alcohols, secondary aliphatic
alcohols, 1,2-alcohols, 1,3-alcohols, 1,5-alcohols, ethylene glycol
alkyl ethers, propylene glycol alkyl ethers, higher homologs
(C.sub.6-C.sub.12) of polyethylene glycol alkyl ethers, N-alkyl
caprolactams, unsubstituted caprolactams, both substituted and
unsubstituted formamides, both substituted and unsubstituted
acetamides, and the like.
Consistent with the formulation of this disclosure, various other
additives may be employed to enhance the properties of the ink
composition for specific applications. Examples of these additives
are those added to inhibit the growth of harmful microorganisms.
These additives may be biocides, fungicides, and other microbial
agents, which are routinely used in ink formulations. Examples of
suitable microbial agents include, but are not limited to,
NUOSEPT.RTM. (Nudex, Inc.), UCARCIDE.TM. (Union carbide Corp.),
VANCIDE.RTM. (R.T. Vanderbilt Co.), PROXEL.RTM. (ICI America), and
combinations thereof.
Sequestering agents, such as EDTA (ethylene diamine tetra acetic
acid), may be included to eliminate the deleterious effects of
heavy metal impurities, and buffer solutions may be used to control
the pH of the ink. From 0.01 wt % to 2 wt %, for example, can be
used. Viscosity modifiers and buffers may also be present, and/or
other additives to modify properties of the ink as desired. Such
additives can be present at from 0.01 wt % to 20 wt %.
The non-Newtonian white inks of the present disclosure can be made
by various methods. However, in one example, a method of making
non-Newtonian white inks is shown and described in FIG. 6, which
provides a flow chart depicting such a method. This method can
include milling 110 a mixture of a white metal oxide pigment having
an alumina coating and a polymeric dispersant in a water-based
carrier to form a pigment dispersion; combining 120 ink vehicle
with the pigment dispersion to form a white ink with suspended
white colorant; and adding 130 amphoteric alumina particles to the
mixture, the pigment dispersion, the white ink, or combination
thereof.
It is noted that when discussing the present inks and/or methods,
each of these discussions can be considered applicable to each of
these examples, whether or not they are explicitly discussed in the
context of that example. Thus, for example, in discussing
refractive index related to a composition or the opacity in the
context of the non-Newtonian white ink, such elements are also
relevant to and directly supported in the context of the methods
described herein, and vice versa.
It is to be understood that this disclosure is not limited to the
particular processes and materials disclosed herein because such
processes and materials may vary somewhat. It is also to be
understood that the terminology used herein is used for the purpose
of describing particular examples only. The terms are not intended
to be limiting because the scope of the present disclosure is
intended to be limited only by the appended claims and equivalents
thereof.
It is be noted that, as used in this specification and the appended
claims, the singular forms "a," "an," and "the" include plural
referents unless the context clearly dictates otherwise.
The term "white metal oxide pigment" refers to pigments that impart
a white color to a ink, but may in fact be essentially colorless
pigments with a high refractive index, e.g., greater than 1.6 or
greater than 1.8. For Example, titanium dioxide (TiO.sub.2) is an
example of such a pigment that imparts white color to an ink, but
when viewed on a particle by particle basis, can appear
colorless.
As used herein, a plurality of items, structural elements,
compositional elements, and/or materials may be presented in a
common list for convenience. However, these lists should be
construed as though each member of the list is individually
identified as a separate and unique member. Thus, no individual
member of such list should be construed as a de facto equivalent of
any other member of the same list solely based on their
presentation in a common group without indications to the
contrary.
Furthermore, it is understood that any reference to open ended
transition phrases such "comprising" or "including" directly
supports the use of other known, less open ended, transition
phrases such as "consisting of" or "consisting essentially of" and
vice versa.
Concentrations, amounts, and other numerical data may be expressed
or presented herein in a range format. It is to be understood that
such a range format is used merely for convenience and brevity and
thus should be interpreted flexibly to include not only the
numerical values explicitly recited as the limits of the range, but
also to include all the individual numerical values or sub-ranges
encompassed within that range as if each numerical value and
sub-range is explicitly recited. As an illustration, a numerical
range of "about 1 to about 5" should be interpreted to include not
only the explicitly recited values of about 1 to about 5, but also
include individual values and sub-ranges within the indicated
range. Thus, included in this numerical range are individual values
such as 2, 3, and 4 and sub-ranges such as from 1-3, from 2-4, and
from 3-5, etc. Additionally, a numerical range with a lower end of
"0" can include a sub-range using "0.1" as the lower end point.
EXAMPLES
The following illustrates some examples of the disclosed inks,
methods, and fluid sets that are presently known. However, it is to
be understood that the following are only illustrative of the
application of the principles of the present disclosure. Numerous
modifications and alternative examples may be devised without
departing from the spirit and scope of the present compositions and
methods. Thus, while the present inks, methods, and fluid sets have
been described above with particularity, the following examples
provide further detail in connection with what are presently deemed
to be some of the acceptable examples.
Example 1
Concentrations of positively charged cationic sites on alumina
surface can be controlled by pH. FIG. 7 shows the impact of pH on
populations of charged species on the surface of alumina exposed to
aqueous environment (exposed to aqueous environment at mildly
acidic or neutral pH range). Thus, electrostatic attraction of
polymeric dispersants having negatively charged anionic anchoring
groups can be controlled through controlling the pH of the cationic
alumina surface. Furthermore, the amphoteric alumina particles also
be similarly impacted.
Example 2
As a general example, a non-Newtonian white metal oxide dispersion
with good sediment redispersibility is prepared by milling base
alumina-coated TiO.sub.2 pigment powder in a water-based slurry
containing about 20-70 wt % of the pigment, 0.5 wt % to 4 wt % (by
dry pigment weight) polymeric non-ionic or predominantly
non-non-ionic dispersant, and 0 to 1 wt % (or 0.1 wt % to 1 wt %)
anionic polymeric dispersant content is between 0.1 and 1% (by dry
pigment weight). Milling can continue until a mean pigment particle
size reaches an appropriate size for light-scattering in a given
formulation.
The non-Newtonian white metal oxide dispersion can then be
formulated into a non-Newtonian white ink by adding additional ink
vehicle components, such as additional water, organic solvent,
surfactant, etc. Solids can be likewise added, such as latex
particles and amphoteric alumina particles as described herein. The
amphoteric alumina particles can have a smaller average size than
the pigments, and can be added at a concentration with the
concentration of the white pigment to generate a non-Newtonian or
shear thinning white ink. By adding amphoteric alumina particles,
lower concentrations of the pigment may be added and still achieve
a non-Newtonian white ink.
Example 3
A slurry was milled that contained TiO.sub.2 pigment powder with an
alumina and silica coating (Ti-Pure.RTM. R706 available from
DuPont) at 51.5 wt %, 0.3 wt % (per dry pigment weight) of a low M
weight anionic polyacrylic acid (Carbosperse.RTM. K-7028 available
from Lubrizol Corporation), and 0.8 wt % (per dry pigment weight)
of a predominantly non-ionic polymeric dispersant with anionic
anchoring groups (Disperbyk.RTM.-190 available from BYK Chemie).
The milling was carried out in a MiniCer.RTM. bead mill available
from NETZSCH Premier Technologies, LLC., Exton, Pa., utilizing YTZ
milling beads with 0.3 mm diameter. The milling duration was about
120 minutes. The mean particle size of the TiO.sub.2 in the milled
dispersion was about 230 nm (as determined by NANOTRACK.RTM.
particle size analyzer, Microtrac Corp., Montgomeryville, Pa.). To
a first Control Dispersion, nothing further was added. To a second
Example Dispersion, 2 wt % (based on dry pigment weight) of
boehmite amphoteric alumina particles (10 nm to 13 nm average
particle size) were added.
Rheology profiles were generated for each dispersion using an
m-VROC capillary viscometer available from Rheosense, Inc. As shown
in FIG. 8, even though both pigments had an alumina and silica
gel-sol coating, the Control Dispersion did not exhibit
non-Newtonian properties, whereas only 2 wt % (based on pigment
weight) of amphoteric alumina particles added to the dispersion
generated an ink with significant non-Newtonian, shear thinning,
properties, i.e. about 5.times. change from 10 sec.sup.-1 to 1000
sec.sup.-1.
Example 4
Four white inks were prepared to evaluate non-Newtonian and
colorant settling properties. The four inks prepared included were
Ti-Pure.RTM. R706 available from DuPont dispersed by a common
polymeric dispersant package and suspended in an ink vehicle.
Specifically, the white inks prepared were: Control White Ink
(without added amphoteric alumina particles), Example White Ink 1
(with 0.5 wt % added amphoteric alumina particles based on pigment
weight), Example White Ink 2 (with 1 wt % added amphoteric alumina
particles based on pigment weight), and Example Ink 3 (with 2 wt %
added amphoteric alumina particles based on pigment weight). The
respective formulations are shown in Table 1, below:
TABLE-US-00001 TABLE 1 Control Example Example Example Ink Ink 1
Ink 2 Ink 3 Components (wt %) (wt %) (wt %) (wt %)
2-methyl-1,3-propanediol 9 9 9 9 2-Pyrrolidinone 16 16 16 16
.sup.1Tergitol .RTM. 15-S-7 1 1 1 1 .sup.2Capstone .RTM. FS-35 1.98
1.98 1.98 1.98 .sup.1Tergitol .RTM. TMN-6 1 1 1 1 Acrylic binder
latex 21.74 21.74 21.74 21.74 (41.4 wt % polymer solids)
.sup.3Disperal .RTM. Alumina -- 2.63 5.26 10.53 Dispersion
(Boehmite Par- ticle Size 10 nm to 13 nm - 19 wt % solids)
.sup.2Ti-Pure .RTM. R706 TiO.sub.2 28.97 28.97 28.97 28.97 (51.8 wt
% solids) dis- persed with Carbosperse .RTM. K-7028 (0.5 wt %) and
Disperbyk .RTM.-190 (0.8 wt %) Water 20.32 17.68 15.05 9.79 Total
100 100 100 100 .sup.1Dow Chemical Company .sup.2DuPont .sup.3Sasol
Germany
Rheology profiles were prepared for the Control Ink and Example Ink
3 using an m-VROC capillary viscometer available from Rheosense,
Inc. As shown in FIG. 9, the Control Ink and Example Ink 3 were
compared for non-Newtonian or shear thinning characteristics.
Essentially, the impact of 2 wt % of boehmite alumina
nano-particles (about 10 nm to 13 nm average size) significantly
enhanced the non-Newtonian characteristic of the respective inks.
For example, the Control Ink behaved more like a low viscosity
Newtonian fluid; whereas after the addition of 2 wt % (based on the
pigment weight) of the boehmite alumina nano-particles, the white
ink acquired non-Newtonian properties (at only about 15 wt %
pigment content), i.e. 10 sec.sup.-1 was more than about 30% higher
than 1000 sec.sup.-1. The non-Newtonian behavior was measured as
the solids were fully dispersed (not settled) in the ink. When
pigment is settled with the amphoteric alumina particles as a
flocculated mass, within the mass where the settling is present,
the non-Newtonian behavior of this portion of the fluid is even
greater.
Furthermore, X-ray photos of sediment in test tubes with
cone-shaped bottoms produced at 7 days of pigment settling for each
White Ink in Table 1 revealed that as the amphoteric boehmite
alumina particles increased in concentration (from 0 wt % to 0.5 wt
% to 1 wt % to 2 wt %), a looser flocculated mass resulted. For
example, solids in the Control ink settled after 7 days at the
bottom of the test tube with a dark mass (in the X-ray) of densely
packed pigment that was not easily resuspendible. As the boehmite
content was increased, less and less of the densely packed pigment
was present.
While the disclosure has been described with reference to certain
examples, various modifications, changes, omissions, and
substitutions can be made without departing from the spirit of the
disclosure. It is intended, therefore, that the present disclosure
be limited only by the scope of the following claims.
* * * * *
References